Process for purification of contaminated water

ABSTRACT

The present disclosure relates to water purification. The teachings thereof may be embodied in processes for removing contaminants from contaminated water. An example process may include: boiling or evaporating a contaminated water to distill the contaminated water; removing a vapor stream from the boiling or evaporating contaminated water; delivering the vapor stream to an oxidation unit; removing additional contaminants from the vapor stream in the oxidation unit; and discharging a purified water stream from the oxidation unit.

TECHNICAL FIELD

The present disclosure relates to water purification. The teachingsthereof may be embodied in processes for purifying contaminated water.For example, they may be employed to purify flowback water and/orproduced water generated in hydraulic fracturing (fracking) operations.

BACKGROUND

Hydraulic fracturing (also referred to as fracking and/or hydrofracking)injects pressurized water, usually containing sand and chemicals (e.g.,surfactants), into wellbores with the intent of stimulating hydrocarbonproduction. This mixture is referred to as fracking fluid. Frackingfluid is injected primarily into shale formations to break apart theshale. The sand enters the resulting cracks, to keep open pathways fornatural gas or oil to flow to the surface. Although the fracking processis used to generate an abundant flow of petroleum products, includingmethane, the process forces significant amounts of contaminated water tothe surface as wastewater.

Wastewater generated in these operations includes both flowback waterand produced water. Flowback water is defined as a mixture of frackingfluid plus formation water (water present in the shale rock formation)and is the first water generated by the well. The chemical compositionof flowback water resembles that of the fracking fluid. Produced waterfollows flowback water and resembles more closely the composition ofwater present in the shale formation. Produced water is generatedthroughout the life of the well, in some cases discharging up to 2,500barrels per day.

Both flowback and produced water are contaminated with a range ofinorganic and organic chemicals and must be treated before releasingthem to the environment. The composition of flowback and produced watervaries from well to well, and also varies over the life of the well.Contaminants in both flowback and produced water may include suspendedsolids, dissolved material, and/or organic matter. Suspended solids mayinclude sand, dirt, and/or insoluble metal complexes. Dissolved materialmay include inorganic cations and anions such as cations of barium,calcium, iron, magnesium, potassium, sodium and strontium, and anions ofcarbonate, chloride and sulfate. The concentration of dissolved materialassociated with produced water can be up to and in excess of to 250,000mg/l. Organic matter may include dissolved compounds and/or dispersedoils. Dissolved compounds comprise organic compounds present in thewater and may include organic acids (e.g., formic and propionic acids),aromatic hydrocarbons (e.g., benzene, ethylbenzene, toluene, and/orxylenes), polyaromatic hydrocarbons, and/or phenols. For the purpose ofthis document, ammonia and amines are referred to as dissolved organiccompounds. Dispersed oils include droplets of oil suspended in flowbackand/or produced water. If allowed to stand for a length of time, thesedroplets will rise to the surface of the water, forming a sheen. Thetotal organic content of flowback and produced water can range up to andin excess of 1,500 mg/l.

A number of processes have been proposed for the treatment of flowbackand produced water generated from oil, gas and oil-gas productionfields. Said processes have included membrane filtration, distillation,evaporation ponds, adsorption and filtration, and chemical oxidation.The diverse composition of flowback water presents a burden onpurification processes. This is because the process must be capable ofremoving suspended solids, dissolved material and organic matter totrace levels that will allow for re-use or release of the treated water.As a result, achieving target levels of purification while meeting costand size constraints proves troublesome.

SUMMARY

The teachings of the present disclosure relate to purifying contaminatedwater. Various embodiments may include treatment of flowback waterand/or produced water generated in hydraulic fracturing (fracking)operations.

In some embodiments, a process for removing contaminants fromcontaminated water may include: boiling a contaminated water to distillthe contaminated water; removing a vapor stream from the boilingcontaminated water; delivering the vapor stream to an oxidation unit;removing additional contaminants from the vapor stream in the oxidationunit; and discharging a purified water stream from the oxidation unit.

In some embodiments, the oxidation unit comprises a thermal oxidizer.

In some embodiments, the oxidation unit comprises a catalytic reactor.

Some embodiments may include adding air to the vapor stream beforedelivering the vapor stream to the oxidation unit.

In some embodiments, a heater adds heat to the vapor stream beforedelivering the vapor stream to the oxidation unit.

In some embodiments, the oxidation unit comprises a catalytic reactoroperated at a temperature between 200° C. and 600° C. with a noble metalcatalyst.

Some embodiments include recovering heat from the purified water streamafter it exits the oxidation unit to supply at least part of the heat tothe contaminated water.

In some embodiments, the contaminated water includes process water froma hydraulic fracturing operation.

Some embodiments may include a system for removing contaminants fromcontaminated water. The system may include: a distillation still boilingcontaminated water to distill the contaminated water; a vent allowing avapor stream to exit the distillation still; an oxidation unit removingadditional contaminants from the vapor stream; and an outlet discharginga purified water stream from the oxidation unit.

In some embodiments, the oxidation unit comprises a thermal oxidizer.

In some embodiments, the oxidation unit comprises a catalytic reactor.

Some embodiments may include an inlet adding air to the vapor streambefore entering the oxidation unit.

In some embodiments, the oxidation unit comprises a catalytic reactoroperated at a temperature between 200° C. and 600° C. with a noble metalcatalyst.

Some embodiments may include a heat exchanger recovering heat from thepurified water stream after it exits the oxidation unit to supply atleast part of the heat to the contaminated water.

Some embodiments may include a heat recovery loop including a heatexchanger with the purified water stream on the hot side and a steamcompressor downstream of the heat exchanger supplying superheated steamto the distillation still for boiling the contaminated water.

In some embodiments, the contaminated water comprises process water froma hydraulic fracturing operation.

Some embodiments may include a process for hydraulic fracturing. Theprocess may include: stimulating production of a hydrocarbon well byinjecting a fracking fluid into a wellbore; recovering a stream of fluidfrom the wellbore; boiling the fluid to distill the fluid; removing avapor stream from the boiling fluid; adding air to the vapor stream;delivering the vapor stream to an oxidation unit; removing contaminantsfrom the vapor stream in the oxidation unit; and discharging a purifiedwater stream from the oxidation unit.

In some embodiments, the oxidation unit comprises a thermal oxidizer.

In some embodiments, the oxidation unit comprises a catalytic reactor.

Some embodiments may include recovering heat from the purified waterstream after it exits the oxidation unit to supply at least part of theheat to the contaminated water.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic drawing illustrating an example system forimplementing the teachings of the present disclosure; and

FIG. 2 is a schematic drawing illustrating an example system forimplementing the teachings of the present disclosure.

The figures are illustrative of example embodiments and do not limit theteachings of the present disclosure as encompassed by the claims formingpart of the application.

DETAILED DESCRIPTION

Various embodiments of the teachings of the present disclosure may use adistillation still to remove suspended and dissolved solids from thecontaminated water and an oxidation unit (e.g., a thermal oxidizerand/or catalytic reactor) to remove organic compounds from the watervapor exiting the distillation still. An oxidation source (e.g., air)may be added upstream of the oxidation unit. Such methods may produce arelatively organic-free process stream which, when it exits theoxidation unit, includes water of an extremely high purity.

Embodiments of the teachings herein may utilize distillation to removesuspended solids and dissolved material from the water, then employ avapor phase oxidation process, such as thermal oxidation or catalyticoxidation, to remove the organic matter present in the water vapor.

FIG. 1 is a schematic drawing illustrating an example system 10 forimplementing the teachings of the present disclosure. In someembodiments, the contaminated water 12 enters system 10 and is deliveredto a distillation still 20. The contaminated water 12 may include acontinuous flow, a periodic flow, and/or discrete batches ofcontaminated water. System 10 may be used to purify water contaminatedwith suspended solids, dissolved material, and/or organic matter,including biological organisms such as bacteria and viruses. Examples ofcontaminated water include, but are not limited to, flowback andproduced water generated during hydrofracturing operations and/or otherdrilling operations. The contaminated water 12 is boiled in distillationstill 20 to remove suspended solids and dissolved material, plus aportion of the organic matter (such as compounds having a boiling pointsignificantly greater than that of water). By boiling the contaminatedwater 12, any bacteria and viruses are expected to be rendered inert.

Within the distillation still 20, the contaminated water 12 is heated toa temperature sufficient to bring about evaporation. Water vapor (steam)and any volatilized organic compounds 24 a exit the top of the still 20.A mixture of suspended solids, dissolved material, and anynon-volatilized organic matter (e.g., high molecular weight oils) 22will remain in the distillation still and can be removed by techniquesknown to one skilled in the art, such as an auger screw, or merelywashed from the distillation still.

The process stream 24 a (water vapor and/or steam) may be heated withheater 28, may be combined with air and/or another oxidation source 26,and delivered to an oxidation unit 30 as process stream 24 b. Theoxidation unit 30 combines the process stream 24 b with one or moreoxidants (e.g., O₂). Any organic matter present in the process stream 24b is expected to be oxidized and thereby removed from the stream ofwater 34 exiting the oxidation unit 30. The oxidation unit 30 mayinclude a thermal oxidizer and/or a catalytic reactor. The purifiedwater vapor 34 exiting the oxidation unit may be condensed andrecovered, or merely vented to atmosphere.

FIG. 2 is a schematic drawing illustrating an example system 40 forimplementing the teachings of the present disclosure. System 40 mayinclude additional components in relation to system 10 that provideincreased energy efficiency. In system 40, contaminated water 42 isdelivered to a distillation still 50. Within the distillation still 50,the contaminated water 42 is heated at least to its boiling point, withwater vapor/steam and/or volatilized organic compounds exiting the topof the still in process stream 54.

System 40 may include a heat exchanger 60. The process stream 54 maypass through a cold side of the heat exchanger 60 to gain thermal energyand/or raise the temperature of process stream 54. After exiting theheat exchanger 60 as heated process stream 62, system 40 may add airand/or another oxidation source, and/or a further heat source 66. Thecombination of heating may raise the process stream 62 to a targetreaction temperature before entering an oxidation unit 70.

Oxidation unit 70 may include a thermal oxidizer and/or a catalyticreactor. The oxidation unit 70 converts any the organic matterassociated with the process stream (via oxidation) to CO₂ and H₂O. Thepurified water vapor 74 exiting the oxidation unit may pass through thehot side of the heat exchanger 60 to recover heat from the purifiedvapor stream 74. Purified vapor stream 66 may be delivered at atemperature suitable for input to a steam compressor 80. Thesuperheated, compressed process stream 82 exiting the steam compressor80 may be delivered to heat exchanger coils 84 located within thedistillation still 50.

In such an embodiment, the compressed, superheated process stream 82 hasa condensation temperature greater than the boiling point of theincoming contaminated water and will thus provide the necessarytemperature gradient to recover the heat of condensation from the watervapor 82. The effluent stream 86 exiting the heat exchanger coils 84will be even further reduced in pressure and/or temperature. Thepurified water may be further cooled and recovered, or alternativelyreleased to the atmosphere. Suspended solids, dissolved material, and/orany non-volatilized organic matter (high molecular weight oils) 52 willremain in the distillation still 50 and can be removed by techniquesknown to one skilled in the art, such as an auger screw, or merelywashed from the distillation still.

Although FIGS. 1 and 2 show an oxidant (e.g., air), blended with thewater vapor stream 24 a, 54, an oxidant may be added at any locationup-stream of the oxidation units 30, 70. For example, air can be addeddirectly to the distillation still 20, 50. In either system, organicmatter volatilized with the steam may be removed from the vapor phaseprocess stream using an oxidation process (e.g., catalytic oxidationand/or thermal oxidation). At the end of the process, water may bevented to atmosphere or alternatively recovered for discharge or re-use.It is possible that the purified water may be high in CO₂ content due tothe solubility of CO₂ in water. If the CO₂ content in the product wateris excessive, the CO₂ content can be reduced to acceptable levels byaerating the water. The example processes described herein yield waterthat is of high purity, namely extremely low in dissolved solids andorganic matter, and essentially free of suspended solids andbacteria/viruses.

Many processes proposed for the purification of contaminated water, suchas produced and flowback water associated with hydrofacturing, areeffective in their ability to remove suspended solids and dissolvedmaterial, but are not able to effectively remove organic matter,especially organic compounds that are soluble in water. Examples oforganic compounds soluble in water include formic acid, benzene,toluene, and phenol. In contrast, the systems and methods describedherein remove organic matter in the vapor phase by, for example, usingoxidative technologies, such as catalytic oxidation and thermaloxidation, which may convert the organic matter to CO₂ and H₂O.

In practice, the systems and the methods of the present disclosure addthe contaminated water to a distillation still which, upon heating,produces steam. Organic matter will often be present in the steam thatexits the still. In order to remove the organic matter, air and/oranother oxidant source is added to the process stream upstream of theoxidation unit. The process stream is heated to an elevated temperaturesufficient to promote oxidation reactions involving the organic matter,such as greater than about 200° C. The heated process stream then entersan oxidation unit, such as a catalytic reactor or a thermal oxidizer.Systems including a catalytic reactor may have a smaller size and/or alower temperature of operation. Within the oxidation unit, the vaporphase organic compounds are oxidized in the presence of an oxidant, suchas O₂, to CO₂ and H₂O. The process stream exiting the oxidation unitcontains purified water in the vapor phase. The purified water vapor maybe released to the atmosphere or, alternatively, condensed for re-use orrelease into streams, lakes, rivers, irrigation systems, etc. Should thecondensed water contain an unacceptable level of dissolved CO₂, thedissolved CO₂ may be removed by techniques known to one skilled in theart, such as aeration.

The processes and systems described herein may be reduce required energyinput. Approximately 450-500 BTU of energy are required to heat onegallon of water from room temperature to its boiling point underatmospheric pressure. In contrast, approximately 7,200 BTU of energy arerequired to transition one gallon of water from the liquid phase to thevapor phase. As such, vaporization of the contaminated water requires asignificant energy input. Additional energy is required to heat thesteam exiting the still and the oxidant to a temperature sufficient tooxidize the vapor phase organic compounds. For example, heating thesteam exiting the still to for example 400° C. (as would be required foran oxidation catalyst) would require an additional 2,000 to 3,500 BTUper gallon water, depending on the amount of oxidant being added. Assuch, recovery of as much energy as possible may reduce the operatingcosts of the processes and systems described herein.

In both systems, the distillation still 20, 50 removes suspended solidsand dissolved material; however, the distillation still 20, 50 will alsoremove bacteria and viruses, plus a portion of the organic matter thathas a boiling point significantly greater than that of water. Theoxidation unit is intended to decompose any organic matter that exitsthe distillation still with the water vapor, converting the organicmatter to CO₂ and H₂O via reactions known to one skilled in the art.Examples of configurations designed to minimize the energy input to theprocess are presented in the following paragraphs. These examples arenot intended to be exclusive but rather to indicate variousconfigurations.

As described above in relation to FIG. 1, the contaminated water 22 canbe added batchwise or continuously. Within the distillation still 20,the contaminated water 22 is heated to a temperature sufficient togenerate water vapor, with the water vapor/steam and volatilized organiccompounds exiting the top of the still in a process stream 24 a. At thispoint, the water vapor is heated, combined with an oxidation source, anddelivered to an oxidation unit 30. The oxidation unit 30 converts theorganic compounds associated with the process stream 24 b to CO₂ andH₂O.

In some embodiments, the purified water vapor 34 exiting the oxidationunit may be delivered directly to heat exchanger coils located withinthe distillation still 20 (not explicitly shown in FIG. 1). In thismanner, the energy associated with high temperature process stream 34exiting the oxidation unit 30 may be recovered. The water vaporassociated with the product stream exiting the heat exchanger coilslocated within the distillation still 30 may be condensed and recovered,or alternatively, vented to atmosphere. Suspended solids and dissolvedmaterial 22 will settle to the bottom of the distillation still 20 andcan be removed by techniques known to one skilled in the art, such as anauger screw, or merely washed from the distillation still. Residualnon-volatilized organic matter (high molecular weight oils) 22 may beremoved at the time the still 20 is cleaned or shut down. For example,said oils may be skimmed from the surface of water present in thedistillation still 20.

In some embodiments, such as that shown in FIG. 2, the water vapor 54exiting the still 50 may be heated to an intermediate temperature bypassing through a heat exchanger 60, combined with air and/or anotheroxidation source 64, then heated to the target operating temperature anddelivered to an oxidation unit 70. The oxidation unit 70 converts theorganic compounds associated with the process stream 62 to CO₂ and H₂Oby reactions known to one skilled in the art. The oxidation unit can bea thermal oxidizer and/or a catalytic reactor. The purified water vapor74 exiting the oxidation unit 70 is delivered back to the heat exchanger60 used to pre-heat the process stream 54. In this manner, the energyassociated with the effluent stream 74 from the oxidation unit 70 isused to pre-heat the feed stream 54 to the oxidation unit 70. Theprocess stream 66 exiting the heat exchanger 60 may be vented toatmosphere. Alternatively, the process stream 66 exiting the heatexchanger 60 may be delivered to heat exchanger coils 84 located withinthe distillation still 50. The purified water vapor 86 exiting the heatexchanger coils 84 may be condensed and recovered, or vented toatmosphere. Suspended solids and dissolved material 52 will settle tothe bottom of the distillation still 50 and can be removed by techniquesknown to one skilled in the art, such as an auger screw, or merelywashed from the distillation still 50. Residual non-volatilized organicmatter (high molecular weight oils) 52 may be removed at the time thestill 50 is cleaned or shut down. At which point, said oils can beskimmed from the surface of any water 42 present in the distillationstill 50.

In some embodiments, the energy associated with the effluent stream 74from the oxidation unit 70 is used to pre-heat the feed stream 54/62 tothe oxidation unit 70. The process stream 66 exiting the heat exchanger66 is delivered to a steam compressor 80. The stream compressor 80compresses the process stream 66 to an elevated pressure, such asgreater than about 3 psig, and, in some embodiments, greater than about15 psig. Compressing the process stream increases the dew pointtemperature of the water vapor, thereby allowing for recovery of theheat of condensation. In the example shown in FIG. 2, the steamcompressor 80 is located downstream of the oxidation unit 70. In someembodiments, the steam compressor 80 may be located upstream of theoxidation unit 70. The pressurized process stream 82 may then bedelivered to a heat exchanger 84 located within the distillation still50. In this manner, a significant amount (e.g., greater than 50%) of theheat of condensation associated with the water vapor may be recovered.

Configurations presented above represent examples and as such do notlimit the scope of the present disclosure. The processes and systems maybe operated batchwise or continuously. Batchwise operation involvesfilling the distillation still with contaminated water, closing thestill, and heating the still to a temperature as necessary to generatewater vapor at a targeted rate. Once the volatile contents of the still(for example, water and organic contaminants) have been removed to thetarget level, such as greater than 90%, the still is cooled, emptied ofbrine, solids, and/or non-volatilized organic matter and the process isrepeated.

In a continuous mode of operation, the distillation still is operated ata target contaminated water level range. Contaminated water iscontinuously added to the distillation still, with the volatilecomponents (primarily water with lower levels of volatile organiccontaminants) boiled away at a rate consistent with that of contaminatedwater additions. Solid material that settles to the bottom of the stillmay be removed continuously, such as by an auger screw. Alternatively,the distillation still may be periodically shut down for the removal ofbrine and solids, plus residual non-volatilized organic matter.

In some embodiments, upstream unit operations may remove all or aportion of the suspended solids prior to the contaminated water enteringthe distillation still. Said operations are known by one skilled in theart and include settling tanks, aeration vessels and filter presses, forexample.

The distillation still removes the suspended solids and dissolvedmaterial from the contaminated water. The distillation still will alsoremove any non-volatilized organic matter, such as high molecular weighthydrocarbons with boiling points significantly greater than that ofwater. As such, the design of the distillation still can vary inconfiguration depending on several factors that include the heatrecovery, heat input, and brine/solid removal, for example. The designand operation of a distillation still is known to one skilled in theart. The distillation still can be heated directly or indirectly usingoil, natural gas, gasoline, and/or kerosene, for example. Alternatively,the distillation still can be electrically heated. In some embodiments,the distillation still includes heat exchanger coils to recover heatassociated with the effluent stream of the oxidation unit. Thedistillation may allow continuous removal of brine and solids thatsettle at the bottom of the still. For example, an auger can be employedto transport the solids from the bottom of the distillation still. Thedistillation still can be operated at or near atmospheric pressure,under vacuum or under pressure. A multi-stage distillation still canalso be employed. The solids that accumulate at the bottom of thedistillation still can be removed on a continuous or periodic basis.

The oxidation unit removes organic compounds from the water vapor thatexits the distillation still. A chemical reaction between the vaporphase organic compounds and an oxidant (such as oxygen) converts theorganic compounds to CO₂ and H₂O. Examples of oxidation units that arecapable of decomposing organic compounds in the vapor phase include athermal oxidizer and a catalytic reactor. The design and operation of athermal oxidizer are known to one skilled in the art. Thermal oxidizersheat the process stream to temperatures of approximately greater thanabout 800° C. as required to oxidize organic compounds present in thewater vapor exiting the distillation still. Thermal oxidizers may be ofa reverse flow design. The size of the thermal oxidizer is dependent onthe flow rate of the process stream, the operating temperature, and thenature of the organic compounds present in the process stream.

A catalytic reactor uses a catalyst to promote oxidation reactionsnecessary to convert organic compounds present in the water vaporexiting the distillation still to CO₂ and H₂O. The size of the catalyticreactor may depend on and/or limit the flow rate of the process stream,the operating temperature of the reactor, the nature of the organiccompounds present in the process stream, and the composition of thecatalyst. The catalyst may be comprised of noble metal or base metal, ormixtures thereof, dispersed upon a high surface area substrate, such asaluminum oxide. Example noble metals include platinum and palladium.Base metals may include copper, iron, and nickel. The design and use ofoxidation catalysts to decompose organic compounds in the vapor phase isknown to one skilled in the art. The catalytic reactor will operate at atemperature necessary to achieve the desired destruction efficiency ofthe organic compounds that exit the distillation still with water vapor.The operating temperature of the catalyst may be as low as below about200° C. or as high as greater than 600° C. In some embodiments, theoxidation unit achieves greater than 75% destruction of organiccompounds present in the water vapor, greater than 90% destruction,and/or more preferably greater than 99% destruction.

A steam compressor may increase heat recovery from the process flow. Insome embodiments, the steam compressor raises the pressure of the steamexiting the catalytic reactor to a point sufficient to raise the dewpoint temperature of the steam to greater than about 5° C. above theboiling point of the contaminated water in the distillation still,and/or greater than about 20° C. above the boiling point of thecontaminated water in the distillation still. In this manner, asignificant amount of the heat of condensation can be recovered in thedistillation still. In some embodiments, the steam compressor can belocated upstream of the oxidation unit. Such an arrangement increasesthe residence time of the process stream in the oxidation unit, therebyreducing the size of the oxidation unit.

An oxidant, such as air, ozone, and/or a mixture thereof, may be addedupstream of the oxidation unit in order to facilitate oxidationreactions to decompose the organic matter present in the vapor phase. Insome embodiments, the oxidant source is added to the distillation still.In some embodiments, the oxidant source is added to the stream exitingthe distillation still at any point upstream of the oxidation unit. Theoxidant source may be pre-heated prior to introduction into the process.The amount of oxidant added to the process upstream of the oxidationunit should be sufficient to completely oxidize the organic contaminantsto CO₂ and H₂O.

Water vapor exiting the processes and systems may be vented toatmosphere. Alternatively, the water vapor exiting the novel process maybe condensed for re-use or release into ponds, streams, rivers, lakes,ground water, etc. CO₂ may be generated as a result of the oxidationreactions. Should the levels of CO₂ in the condensed water beunacceptable, an additional process may be necessary in order to removethe dissolved CO₂. For example, the condensed, purified water may beaerated.

It is possible that organic compounds containing fluorine, chlorine,bromine, sulfur, and/or mixtures thereof, may be present with the watervapor exiting the distillation still. Said compounds, examples of whichinclude halogenated organic compounds, mercaptans and hydrogen sulfide,may react within the oxidation unit to yield products that may includemineral acids, examples of which include HCl, HF, HBr, and/or H₂SO₄.Should this be the case, an acid gas abatement unit, such as a solidadsorber designed to remove acid gases, may be used. Otherwise, theproduct water may not be of a suitable pH for release to the atmosphereor reuse/release.

EXAMPLES

A pilot scale process was constructed to assess the effectiveness of theproposed process to purify water contaminated with salts, suspendedsolids, and organic compounds. The pilot scale process included adistillation still and a catalytic reactor. The process was operated byadding the contaminated water to the distillation still, heating thecontaminated water to its boiling point, adding air to the water vapor,and diverting the resulting process stream to a catalytic reactor. Thecatalytic reactor was operated at between 350° C. and 400° C. andemployed a supported noble metal catalyst in the form of a monolith. Thepilot scale process generated approximately 250 ml purified water perhour. Air was added to the process stream exiting the distillation stillat a flow rate of 1 Nl/min (Nl is defined as normal liter and refers to1 liter of gas at 1 atmosphere pressure, 0° C.). The process gas exitingthe catalytic reactor was delivered to a condenser in order to recoverthe water for evaluation purpose. A portion of the effluent stream wasdelivered to a gas chromatograph for analysis of CO₂, which was used toverify the oxidation reactions. Product purified water was analyzed forresidual solids and organic compounds.

Example 1 Comparative

A produced water sample was obtained from the Utica shale oil fields.The water was mixed and a sample was analyzed for total organic contentand solids content (suspended solids and dissolved material). The totalorganic content of the mixture was determined to be on the order of 450mg/l. The solids content was on the order of 15%. Solids were comprisedof sodium, calcium, iron, zinc, iron, phosphorous and chlorine.

1.0 liters of the produced water was loaded into a pilot scaledistillation still. The water in the distillation still was heated toboil, which required approximately 30 minutes to achieve. Once at boil,water in the distillation still was evaporated at a rate ofapproximately 320 ml/min. Water vapor from the distillation still wasdelivered to a condenser, where product liquid water was recovered. Uponcompletion of the distillation operation, an oily sheen was observed onthe surface of the product water. The total dissolved solids (TDS)content of the product water was 82.5 ppm. The organic content of theproduct water was 192 mg/liter.

Example 2

1.0 liters of the produced water sample of Example 1 was loaded into thepilot scale distillation still. 1.0 Nl of air were pre-heated toapproximately 100° C. and delivered to the top of the distillation stillas an oxidant source for the catalyst. The process stream exiting thedistillation still was delivered to a catalytic reactor, then to acondenser. The catalytic reactor was housed in a tube furnace and heatedto approximately 400° C. Approximately 39 cm³ of a supported noble metaloxidation catalyst, in the form of a monolith, was located within thecatalytic reactor for the purpose of oxidizing the organic compounds toCO₂ and water vapor. Under operating conditions, the residence time ofthe process stream through the catalyst is approximately 0.27 seconds. Aportion of the effluent stream was delivered to a gas chromatograph forCO₂ analysis.

The water in the distillation still was heated to boil, which requiredapproximately 30 minutes to achieve. Once at boil, water in thedistillation still was evaporated at a rate of approximately 320 ml/min.CO₂ was detected in the effluent stream throughout the duration of therun. Upon completion of the distillation operation, no oily sheen wasobserved on the surface of the product water. Examination of thedistillation still revealed a significant amount of solid material. Theproduct water was analyzed using solvent extraction techniques for theconcentration of hydrocarbons. Results of the analysis indicated that towithin the detection limits of the methodology, no organic compoundswere associated with the product water. The total dissolved solid (TDS)content of the product water was measured to be 43.2 ppm. Resultsdemonstrate that the described process produces high purity water.

The pH of the product water was measured to be 9.05. Air was bubbledthrough the product water for 1 hour in order to remove dissolved CO₂.Upon completion of the aeration process, the pH of the water wasmeasured to be 7.11. This result demonstrates that dissolved CO₂ canreadily be removed from the product water by aeration.

Example 3

2.0 liters of the produced water sample of Example 1 was loaded into thepilot scale distillation still. 1.0 Nl of air were pre-heated toapproximately 100° C. and delivered to the top of the distillation stillas an oxidant source for the catalyst. The process stream exiting thedistillation still was delivered to a catalytic reactor, then to acondenser. The catalytic reactor was housed in a tube furnace and heatedto approximately 400° C. Approximately 39 cm³ of a supported noble metaloxidation catalyst, in the form of a monolith, was located within thecatalytic reactor for the purpose of oxidizing the organic compounds toCO₂ and water vapor. Under operating conditions, the residence time ofthe process stream through the catalyst is approximately 0.27 seconds. Aportion of the effluent stream was delivered to a gas chromatograph forCO₂ analysis.

The water in the distillation still was heated to boil, which requiredapproximately 30 minutes to achieve. Once at boil, water in thedistillation still was evaporated at a rate of approximately 320 ml/min.Upon completion of the operation, the distillation still was emptied toremove the residual solids, and the operation was repeated a total of 20times in order to assess the durability of the catalyst. Selected watersamples, including the first and last, were analyzed for total dissolvedsolids (TDS), organic content and pH following aeration. For all watersamples, the TDS never exceed 50 ppm and to within the detection limitsof the instruments, no organic compounds were detected. For all samples,the pH of the product water following aeration never exceeded 7.7.

What is claimed is:
 1. A process for removing contaminants fromcontaminated water, the process comprising: boiling or evaporating acontaminated water to distill the contaminated water; removing a vaporstream from the boiling or evaporating contaminated water; deliveringthe vapor stream to an oxidation unit; removing additional contaminantsfrom the vapor stream in the oxidation unit; discharging a purifiedwater stream from the oxidation unit; exchanging heat from the purifiedwater stream leaving the oxidation unit to the removed vapor streambefore the removed vapor stream enters the oxidation unit.
 2. A processaccording to claim 1, wherein the oxidation unit comprises a thermaloxidizer.
 3. A process according to claim 1, wherein the oxidation unitcomprises a catalytic reactor.
 4. A process according to claim 1,further comprising adding air to the vapor stream before delivering thevapor stream to the oxidation unit.
 5. A process according to claim 1,further comprising a heater adding heat to the vapor stream beforedelivering the vapor stream to the oxidation unit.
 6. A processaccording to claim 1, wherein the oxidation unit comprises a catalyticreactor operated at a temperature between 200° C. and 600° C. with anoble metal catalyst.
 7. A process according to claim 1, wherein thecontaminated water includes process water from a hydraulic fracturingoperation.
 8. A process for hydraulic fracturing, the processcomprising: stimulating production of a hydrocarbon well by injecting afracking fluid into a wellbore; recovering a stream of fluid from thewellbore; supplying heat to the fluid to distill the fluid by boiling;removing a vapor stream from the boiling fluid; adding air to the vaporstream; delivering the vapor stream to an oxidation unit; removingcontaminants from the vapor stream in the oxidation unit; discharging apurified water stream from the oxidation unit; and exchanging heat fromthe purified water stream leaving the oxidation unit to the removedvapor stream before the removed vapor stream enters the oxidation unit.9. A process according to claim 8 wherein the oxidation unit comprises athermal oxidizer.
 10. A process according to claim 8, wherein theoxidation unit comprises a catalytic reactor.